Epoxy resin compositions containing tetraphenylborates of imidazoles

ABSTRACT

This invention provides an epoxy resin composition excellent in curability and storage stability (shelf life or potting life) and capable of yielding a cured product excellent in various characteristics, comprising an epoxy resin and a tetrasubstituted borate of imidazoles incorporated therein, and also provides a method for manufacturing said composition.

United States Patent [191 Ogata et al.

[451 Sept. 30, 1975 EPOXY RESIN COMPOSITIONS CONTAINING TETRAPHENYLBORATES OF IMIDAZOLES [75] Inventors: Masatzugu Ogata, Hitachi; Ritsuro Tada, Mito; Motoyo Wajima, Hitachi; Masahiro Kitamura, Hitachi; l-Iiroshi Suzuki, Hitachi; Mikio Sato, Hitachi; Etuzi Kubo, Shimodate, all of Japan [731 Assignees: Hitachi, Ltd.; Hitachi Chemical Company, Ltd., Japan 221 Filed: Mar. 27, 1974 21 App]. No.: 455,403

[52] US. Cl. 260/37 EP; 260/2 EP; 260/18 EP; 260/23 EP; 260/47 EN; 260/51 EP 51 m. cm C08L 63/00 581 Field of Search 260/37 EP, 47 EN, 47 EC, 260/2 N, 309

[56] v References Cited UNITED STATES PATENTS 3,678,007 7/1972 Dowbenko et a] 260/2 N X 3,793,247 2/1974 Fleming et al. 260/2 N X Primary E.ran1it1erLewis T. Jacobs Attorney, Agent, or FirmCraig & Antonelli [5 7] 1 ABSTRACT 17 Claims, No Drawings EPOXY RESIN COMPOSITIONS CONTAINING TETRAPHENYLBORATES OF IMIDAZOLES Epoxy resins are preferred for such rather diversified uses as casting, molding, laminating, impregnating, adhering, and coating. The methods for curing epoxy resins can be broadly classified into the following three: The first method uses mainly acid anhydride curing agents, the second method uses amine-type curing agents, and the third method uses such curing agents as boron trifluoride-amine complexes and imidazoles. These methods, however, have the following disadvantages: In the first method which utilizes acid anhydride curing agents, since heating at a considerably elevated temperature for a considerably long period of time is necessary in curing, a curing catalyst, such as tertiary amine or a quaternary ammonium salt is added in order to shorten the curing time. The addition of such a curing catalyst has a disadvantage of causing a marked decrease in storage stability of the resulting epoxy resin composition. On the other hand, although the second method utilizing amine-type curingagents has an advantage of easily yeilding a cured product superior in moisture resistance, chemical resistance, electrical and mechanical properties to that obtained with acid anhydride curing agents, it has a disadvantage in that owing to low reactivity of the amine-type curing agent used in an epoxy resin composition of desirable storage stability, the curing agent is generally used together with a curing catalyst such as, for example, a'modified amine, a boron trifluoride-amine complex, phenol, chlorophenol, bisphenol-A, resorcinol, phenol resin, salicylic acid, metal salts of salicylic acid, and triphenyl phosphite. However, the addition of the curing catalyst results, as mentioned above, in a marked reduction in shelf life or potting life at around room temperature, an insufficient cure-promoting effect, or a deterioration in moisture resistance, chemical resistance, and electrical and mechanical properties. In short, among conventional acid anhydrides and amine compounds, there are no compounds capable of statisfying all of the requirements for curability, and storage stability of the epoxy resin composition and for various characteristics of the cured product. When a certain boron trifluoride-amine complex is used as the curing agent, it has already been known that an epoxy resin composition having a good storage stability is obtained, whereas the moisture resistance is yet to be improved. I

An object of this invention is to provide an epoxy resin composition excellent in so-called latent curability, that is, having a good storage stability Without gelling at room temperature or thereabout, and rapidly curing on heating.

Another object of this invention is to provide an epoxy resin composition which yields on curing a cured product excellent in electrical, mechanical and other characteristics, particularly in moisture resistance and chemical resistance.

A further object of this invention is to provide an epoxy resin composition suitable as a material for use in casting, laminating, impregnating, adhering, coating, and molding.

A still further object of this invention is to provide an epoxy resin composition suitable for electrical insulation, particularly for encapsulating a semiconductor device and also suitable as a prepreg for use in laminated resin sheet-and in adhering.

A still further object of this invention is to provide an epoxy resin composition susceptible to wet mixing (mixing in the softened or molten state).

A still further object of this invention is to provide a method for manufacturing an epoxy resin composition, whereby simplification of the working and enhancement in productivity can be achieved.

Other objects. and advantages of the invention will become apparent from the following description.

The epoxy resin composition of this invention is characterized in that it consists essentially of (a) parts by weight of an epoxy resin having at least two vicinal epoxy groups and (b) 0.01 to 30 parts by weight of at least one organoboron compound selected from the group consisting of tetra-substituted borates of imidazole and tetra-substituted borates of imidazole derivatives obtained by reacting alkali metal salts of tetrasubstituted boron compounds with at least one member selected from the group consisting of salts of imidazole and salts of imidazole derivatives formed by reacting acids with imidazole and imidazole derivatives represented by the general formula:

wherein R R R and R which may be the same as or different from one another, are selected from the group consisting of hydrogen, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, acyl group having 2 to 7 carbon atoms, aryl groups having 6 to 12 carbon atoms, cycloalkyl groups having 6 to 12 carbon atoms, cycloalkenyl groups having 6 to 12 carbon atoms, aldehyde group, 'carboxyl group, cyano group, and nitro group.

The most characteristic feature of this invention consists in that at least one organoboron compound se lected from the group consisting of the tetrasubstituted borates of imidazole and its derivatives (these salts are hereinafter referred to simply as ITPB) represented by the general formula (1) wherein R R R R and R are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, acyl groups having 2 to 7 carbon atoms, aryl groups having 6 to 12 carbon atoms, cycloalkyl groups having 6 to 12 carbon atoms, cycloalkenyl groups having 6 to 12 carbon atoms, aldehyde groups, carboxyl groups, cyano groups, or nitro groups (said R R R R and R may be the same as or different from one another), and R is a phenyl group or a substituted phenyl group. The general formula (1), however, is not yet established but only presumed.

The method of preparing the said ITPB has no particular limitation. An example of the preparative procedure is given below.

ITPB is obtained by reaction of two starting components, that is, a salt of an imidazole of the formula (2) wherein R,, R R R and R are the same as defined above, and X is an anion such as chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, or acetate ion, and a tetra-substituted borate of the formula (3) wherein M is an alkali metal ion such as lithium ion, sodium ion, or potassium ion, and R is the same as defined in the formula (2).

The salts of imidazoles can be prepared by reacting an imidazole such as, for example, imidazole, 2-

methylimidazole, 2-undecylimidazole, 2- heptadecylimidazole, 2-phenylimidazole, 2-ethyl-4- methylimidazole, 1-benzyl-2-methylimidazole, 1-

cyanoethyl-2-methylimidazole, l-cyanoethyl-2-ethyl-4- methylimidazole l-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-Z-phenylimidazole, with at least one acid selected from the group consisting of inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as acetic acid, oxalic acid, and succinic acid; acidic aromatic nitro compounds such as picric acid and picrolonic acid; and alkyl halides, in water or in an organic solvent such as an alcohol, at room temperature or elevated temperatures. The intended ITPB is obtained by reacting a salt of an imidazole and an alkali metal salt of tetra-substituted boron in water or in an organic solvent such as an alcohol, at room temperature or elevated temperatures. Examples of useful ITPB include imidazolium tetraphenylborate, methylimidazolium tetraphenylborate, 2-ethyl-4- methylimidazolium tetraphenylborate, 2-ethyl-1,4- dimethylimidazolium tetraphenylborate, l-cyanoethyl- 2-ethyl-4-methylimidazolium tetraphenylborate, 1- cyanoethyl-2-undecylimidazolium tetraphenylborate, l-cyanoethyl-Z-phenylimidazolium tetraphenylborate, l-vinyl-2 -methylimidazolium tetraphenylborate, 1- vinyl-2,4-dimethylimidazolium tetraphenylborate, l-B- hydroxy-ethyl-2-methyl-imidazolium tetraphenylborate, 1-allyl-2-methylimidazolium tetraphenylborate, l-allyl-2-phenylimidazolium tetraphenylborate, and lallyl-2-undecylimidazolium tetraphenylborate. These compounds may be used alone or in admixture of two or more.

Preperation Examples of ITPB are shown below, but the invention is not limited to the Examples, and, for example, reaction conditions and others may be modified at will.

Preparation Example 1 In 300 ml of water was dissolved 0.85 g of imidazole. To the resulting solution was added 1.2 ml of concentrated hydrochloric acid to allow the reaction to proceed, to fonn a compound of the formula (2). To the reaction mixture was added with stirring 50 ml of an aqueous solution of 4.3 g of sodium tetraphenylborate to allow the reaction to proceed, to obtain 4.5 g of the intended imidazolium tetraphenylborate (as white precipitate) having a melting point of to 188C.

Preparation Example 2 In 300 ml of water was dissolved 1.6 g of 2-ethyl-4- methylimidazole. To the solution was added 1.2 ml of concentrated hydrochloric acid to allow the reaction to proceed, to form a compound of the formula (2). To the solution was added with stirring 50 ml of an aqueous solution of 4.3 g of sodium tetraphenylborate to allow the reaction to proceed, to obtain 55 g of the intended 2-ethyl-4-methylimidazolium tetraphenylborate (as white precipitate) having a melting point of 186- 190C.

Preparation Example 3 Preparation Example 4 In 300 ml of methyl alcohol was dissolved 2.4 g of 1- cyanoethyl-2-undecylimidazole. To the solution was added 0.8 ml of concentrated hydrochloric acid to allow the reaction to proceed, to form a compound of the formula (2). To the reaction mixture was added with stirring 50 ml of an aqueous solution of 2.9 g of sodium tetraphenylborate to allow the reaction to proceed, to obtain 5.0 g of the intended l-cyanoethyl-2- undecylimidazolium tetraphenylborate (as white precipitate) having a melting point of 95 98C.

Preparation Example 5 In 300 ml of methyl alcohol was dissolved 2.2 g of 1- cyanoethyl-2-ethyl-4-methylimidazole. To the solution was added 1.2 ml of concentrated hydrochloric acid to allow the reaction to proceed, to form a compound of the formula (2). To the reaction mixture was added with stirring 50ml of an aqueous solution of 4.3 g of sodium tetraphenylborate to allow the reaction to proceed, to obtain 6.0 g of the intended l-cyanoethyl-Z- ethyl-4-methylimidazolium tetraphenylborate (as white precipitate) having a melting point of 160 162C.

Preparation Example 6 In 100 ml of methyl alcohol was dissolved 1.2 g of 2- ethyl-4-'methylimidazole. To the solution was added 1 .5 g methyl iodide and the mixture was refluxed for about 3 hours. After completion of the reaction, the excess methyl iodide and the methyl alcohol were removed by distillation to obtain a compound of the formula (2). The resulting compound was again dissolved in 300 ml of methyl alcohol. To the solution was added with stirring 50 ml of an aqueous solution of 3.4 g of sodium tetraphenylborate to allow the reaction to proceed, to obtain 4.5 g of the intended 2-ethyl-1,4-dimethylimidazolium tetraphenylborate (as white precipitate) having a melting point of 233 236C.

The amount of the above-said ITPB to be used has no particular limitation. In ordinary cases, it is sufficient to use ITPB in a proportion of 0.01 to 30 parts by weight per 100 parts by weight of the epoxy resin. When the epoxy resin is to be cured with the above-said ITPB alone, particularly preferable is the range of from 0.5 to parts by weight per 100 parts by weight of the epoxy resin. When the amount of ITPB is kept in the said range, the resulting composition is excellent in storage stability, and also in curability at practicable curing temperatures, and the cured product obtained has desirable characteristics. The composition comprising an epoxy resin and ITPB may be further blended with a curing catalyst for use in epoxy resins. By the addition of a small amount of such a curing catalyst, a great effect on acceleration of curing is obtained. Examples of the curing catalysts are boron trifluorideamine complexes, tertiary amines, and organometal salts. These catalysts may be used alone or in admixture of two or more. It is sufficient to use the curing catalyst in an amount in the range of 0.01 to 20 parts by weight per 100 parts by weight, depending, to some extent, on the type of catalyst. Although the curing catalyst may be used in larger amounts, the cured product becomes vinferior in characteristic properties.

In this invention, the aforesaid ITPB can be incorporated into a known epoxy resin-acid anhydride curing agent system, epoxy resin-amine-type curing agent system, and in other epoxy resin compositions obtained by blending an initial condensation product of synthetic resins such as phenol resin, urea resin, and melamine resin; a polyamide resin; or a polysulfide resin with an epoxy resin. By such additional incorporation of ITPB, the curing time at an elevated temperature can be greatly shortened without deteriorating the characteristics inherent in the resin composition. Examples of ouring agents of the acid anhydride type are maleic anhydride, dichloromaleic anhydride, dodecenylsuccinic anhydride, pyromellitic dianhydride, trimellitic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, and hexachloroendomethylenetetrahydrophthalic anhydride. These anhydrides may be used alone or in admixture of two or more. Examples of the amine-type curing agents are aliphatic polyamides such as polymethylenediamine, polyetherdiamine, iminobispropylamine, bis(hexamethylene)triamine, tetraethylenepentamine, and dimethylaminopropylamine;

LII

cycloaliphatic polyamines such as menthanediamine, N-aminoethylpiperazine, and 1,3-diaminocyclohexane; aliphatic amines having an aromatic ring such as tetrachloro-p-xylenediamine: aromatic amines such as mphenylenediamine, diaminodiphenyl ether, diaminodiphenylmethane, 4,4-diaminodiphenylmethane-3 ,3 dicarbonic acid, diaminodiphenyl sulfone, benzidine, 4,4'-bis(o-toluidine), 4,4'-thiodianiline, dianisidine, methylenebis( o-chloroaniline bis( 3 ,4- diaminophenyl) sulfone, and diaminoditolyl sulfone; and dicyanidiamide. These amines may be used alone or in admixture of two or more.

The aforesaid ITPB imparts rapid-curing property to the system comprising an epoxy resin and the abovenoted curing agent, and a more striking effect is obtained particularly with a system comprising an aromatic amine curing agent which has a relatively low reactivity to an epoxy resin because of its low basicity, steric hindrance due to the aromatic ring, and formation of a high-melting solid in the B-stage during the progress of cure. In this case, the shelf life or potting life of the composition at around room temperature is far superior to that of a conventional composition.

The amount of the acid anhydride type curing agents or the amine type curing agents has no special limitation and can be determined in accordance with the formulation of a conventional epoxy resin composition. It is desirable to use an acid anhydride or amine curing agent in such an amount that the ratio of epoxy equivalent to acid anhydride equivalent or amine equivalent becomes 1 0.1 0.5. However, if necessary, the said ratio may be varied in a range of 1 0.001 to 2.0. In this invention, when ITPB is used together with the abovesaid curing agent, the amount of ITPB used has no particular limitation. ln ordinary cases, the object of the invention is sufficiently achieved by using 0.01 to 20 parts by weight of ITPB per parts by weight of the epoxy resin. The amount of ITPB is preferably 0.5 to 5, particularly preferably 2 to 3, parts by weight per 100 parts by weight of the epoxy resin. If ITPB is used in too small an amount, a desirable curing rate is unobtainable, whilst if it is used in excess, not only the composition becomes inferior in some degree shelf life or potting life, but also the cured product tends to decrease in thermal stability and chemical resistance.

The term epoxy resin used herein means a whole range of hitherto known epoxy resins including bisphenol-based epoxy resins such as those obtained from bisphenol-A and epichlorohydrin; novolac-based epoxy resins obtained by reacting epichlorohydrin with a novolac resin; polyphenol-based epoxy resins obtained by reacting epichlorohydrin with condensates of phenols and xylene resins or toluene resins formed by reaction between xylene and formalin or between toluene and paraformaldehyde, respectively; polyhydroxybenzenebased epoxy resins obtained by reacting epichlorohydrin with polyhydric phenols such as resorcinol and hydroquinone; epoxy resins obtained by reacting epichlorohydrin with aromatic or aliphatic carboxylic acids; epoxy resins obtained from vinyl polymers; epoxy resins obtained from polyhydric alcohols such as glycerol; epoxy resins obtained from cycloaliphatic compounds such as cyclohexene, cyclopentadiene, and dicyclopentadiene; epoxy resins obtained from the naturally occuring products such as starch and unsaturated higher fatty acids; nitrogen-containing epoxy resins obtained from aniline or aliphatic amines; epoxy resins having a nitrogen-containing hetero ring obtained from isocyanuric acid; silicon-containing epoxy resins obtained by reacting a silanol with epoxy resins; siliconcontaining epoxy resins obtained by oxidation of silicon-containing compounds having carbon-to-carbon double bonds; epoxidized phospherous esters obtained by epoxidizing phospherous esters having olefinic unsaturation with peracetic acid; and epoxy resins containing in the form of a chelate heavy metal other than silicon and phosphorus. These epoxy resins may be used alone or in admixture of two or more.

The epoxy resin composition of this invention may be incorporated with other synthetic resins such as, for example, phenolic resins and melamine resins; powdered fillers such as, for example, glass, quartz glass, mica, calcium carbonate, calcium sulfate, barium sulfate, alumina, talc, clay, zirconium silicate (zircon), zirconium oxide, lithium aluminum silicate, beryl, aluminum silicate, beryllia, calcium silicate, and silica; flexibilizers such as, for example, polyethylene glycol, dimer acid, dodecenylsuccinic anhydride, polyamide resins, polysulfide resins, and urethane elastomers; releasing agents such as, for example, stearic acid, metal salts of stearic acid, silicone oils, silicone greases, fatty acids, fatty acid esters, and naturally occurring waxes; diluents such as, for example, olefin oxides, glycidyl methacrylate, cyclohexene vinyl monoxide, styrene oxide, phenyl glycidyl ether, butadiene oxide, diglycidyl ether, bis(2,3-epoxycyclopentyl) ether, and divinylbenzene dioxide; surface coupling agents such as, for example, 'y-glycidoxypropyltrimethoxysilane, vinyltrichlorosilane, and n-(trimethoxysilylpropyl)ethylenediamine; or colorants such as, for example, carbon black, titanium oxide, antimony oxide, Cadmium Red, Toluidine Red, l-Iansa Yellow, powdered iron oxide, Phthalocyanine Blue, and Phthalocyanine Green. The amount of the above-noted additives used can be determined according to that conventionally used for respective purposes.

The epoxy resin composition of this invention is very useful, as mentioned hereinbefore, as a material for casting, molding, laminating, impregnating, adhering, and coating. Moreover, as a result of further investigations, the present inventors have found that the present composition is veryr effective when used as a material for encapsulating various semiconductor devices. When a conventional epoxy resin composition is used in encapsulating a semiconductor device, owing to a curing catalyst contained in the composition, a channel is generated at the time of use of the semiconductor device, whereby a leakage current is emitted which markedly decreases the reliability of the device. Such a tendency becomes more pronounced in a device having more sensitive surface such as field effect transistor (PET), and in a device exposed to higher temperatures. To the contrary, such a tendency is insignificant with the present epoxy resin composition. In encapsulating a semiconductor device by use of the present epoxy resin composition, the parasitic channel generation can be effectively suppressed by incorporating in the composition an organic zinc compound as an additive. Examples of useful organic zinc compounds include zinc salicylate, zinc octoate, zinc stearate, zinc ethylenediaminetetraacetate, zinc acetate, zinc terephthalate, zinc lactate, zinc ethylphenyldithiocarbamate, 2-mercaptobenzothiazole zinc salt, and the like. The amount of organic zinc compound to be incorporate is preferably 0.1 to by weight based on the total weight of the epoxy resin composition, because if the incorporated amount is less than 0.1 by weight, the effect of addition becomes practically insignificant, whilst if the 5 amount exceeds 5 by weight, the cured material (encapsulating resin (layer) becomes higher in linear thermal expansion coefficient (a) and lower in mechanical strengths, particularly in brittleness.

As a result of extensive investigations, the present inventors have found that when ITPB and an amine-type curing agent are jointly used, the epoxy resin composition becomes susceptible to wet mixing; in other words, the resin component in the softened or molten state may be mixed together with ITPB and an amine-type curing agent. To the contrary, when a conventional solid epoxy resin incorporated with an amine-type curing agent is mixed at 60 to 85C., curing reaction begins to take place during the mixing operation even if a relatively stable boron trifluorideamine complex is used as the curing agent, thus resulting in an epoxy resin composition having a shelf life or patting life too short for practical uses. Therefore, that an epoxy resin composition can be wet-mixed, as is the case with the present composition, is a novel fact which has never been observed. The industrial advantage of such a com position is manifested in simplification of the operation and in increased productivity. In this invention, the necessary conditions for wet mixing are such that the mixing temperature is 40 to 85C. and the solid epoxy resin in the softened or molten state is mixed while applying a shearing force. The shearing force can be applied by use of various means including as representatives a mixing roll, Ko-kneader extruder, ribbon mixer, extruder, and the like.

The present inventors have confirmed that various combinations of the aforesaid components achieve the object of this invention. Several of the combinations are shown in the following Examples.

EXAMPLE 1 COMPARATIVE EXAMPLE 1 In 100 parts by weight of Epikote 828 was incorpo rated 2 parts by weight of 2-ethyl-4-methyl-imidazole (Sample No. 3), or 10 parts by weight of boron trifluoride-piperidine complex (Sample No. 4), or 5 parts by weight of boron trifluoride-monoethylamine complex (Sample No. 5) each as a known curing agent to prepare three samples of known epoxy resin compositions. In Tables 1 and 2, there are shown gel time at 150C. and 120C., potting life when stored at 40C., and the ratio of potting life to gel time. The potting life is a measure of the storage stability of a resin composition and shown in terms of hours or days which had elapsed until the viscosity of a resin composition reached a value ten times the initial viscosity value (viscosity of the composition immediately after preparation).

Table 1 (Example I) Potting Sample Gel time (hour) life Potting life/gel time No. ITPB 150C. 120C. I (hour) G 150C. G 120C.

2-Ethyl-4-methyll imidazolium tetraphenyl- 0.8 0.5 550 688 110 borate l-Cyanoethyl-Z-phenyl- 2 imidazolium tetraphenyl- 0.9 5.5 480 533 87 borate Table 2 EXAMPLE 2 An epoxy resin composition (varnish) was prepared ;g gzz I) by uniformly mixing 75 parts by weight of an epoxy Sample Gel time (hour) life Potting life/gel time novolac-type epoxy resin (Epikote 154, Shell Chemical 150C (hour) G 150C 120C Co.; epoxy equivalent, 176 181), parts by weight 3 03 L2 45 150 38 of a blsphenol-A-based epoxy resin (Epikote 1001, 4 0.4 5.0 110 2 5 is 20 Shell Chemical Co.; epoxy equivalent, 450 500), 3 5 0.2 1.5 505 2525 337 Note: In the column of potting life/gel time in Table l and Table 2, G 150C. means the ratio of potting life to gel time at 150C., and G 120C. means the ratio of potting life to gel time at 120C. The said ratio is a measure of the latent curability.

Sample No. 1 (Example 1) and Samples No. 3 and 5 (Comparative Example 1) were cured by heating at 120C. for 6 hours and at 1503C. for 15 hours. The mechanical properties of the cured samples were shown in Table 3, and the electrical properties in Table 4.

Table 3 (measured at l0OC.)

parts by weight of 2-ethyl-4-methylimidazolium tetraphenylborate, and 100 parts by weight of methyl ethyl ketone as solvent. The resulting varnish was stable for more than 3 months at 25C., indicating a favorable storage stability.

A piece of insulating mica tape composed of composite mica, 1 mm in thickness, backed with nonwoven polyester fabric, 0.05 mm in thickness, was impregnated with the varnish obtained above and dried in a drying oven at 120C. for about 5 minutes to obtain a prepreg mica insulating tape. The amount of impregnated varnish was 30 to by weight as solids. The prepreg tape obtained was wound in 5 layers around a flat type copper wire (coil conductor), 3 mm X 20 mm l Elongation f 35 X 300 mm, and cured by heating at 150C. for 1 hour Sample g/ 0 g/ to obtain a model coil. The model coil was provided 1 345 4'0 15 X with exterior electrodes and measured for temperature 3 300 2.5 1.5 x 10 characteristics and voltage characteristics of tan 6. The 5 275 16 L2 X results obtained were as shown in Table 5 and Table 6.

Table 4 Item of test Tan8(%) e p(O-cm) Sample No. 25C. 80C. 120C. 25C. 80C. 120C. 25C. 80C. 120C.

1 0.7 1.5 6.9 3.5 3.8 4.0 1.2 x 10 3.5 x 10' 5.5 x 10" 3 0.7 3.0 10 3.6 4.0 4.4 1.5 x 10 2.0 x 10 1.0 x 10 5 0.7 2.6 10 4.9 5.2 6.5 4.5 x 10" 6.0 x 10 8.0 10

Note: in Table 4, tan 6 and s were obtained by measurement at 60 Hz.

Table 5 From the results shown in Table l and Table 2, it is I seen that as compared with an imidazole (Sample No. zgl zziii g 3) and boron trifluoride-piperidine complex (Sample measurement (C.) Tan 8 No. 4), the imidazolium tetra-substituted borates (Samples No. l and No. 2) show a high reactivity at el- Z8 8;: evated temperatures and a prolonged potting life at low 100 2.0 temperatures, indicating their superior latent curabily' Boron trifluoride'monoethylamine complex Note: Measured at a voltage of 2 kV and a frequency of 50 Hz. ple No. 5) is superior in latent curability to Samples Table 6 No. l and No. 2, whilst markedly inferior in mechanical and electrical properties of the cured product, as is ap- Voltage of measurement tan parent from the results shown in Table 3 and Table 4. i 8:; The said complex presents, in addition, a serious prob- 6 1.2 lem with respect to moisture resistance of the cured 5:8

product, as disclosed hereinafter.

Note: Measurement was made at 20C. and a freqtlefly til" 50 H2.

The dielectric breakdown voltage of the model coil was about to kV/mm (20C.).

The flexural strength was measured on a cylindrical mica tape cured layer prepared by removing the coil conductor from the model coil. The results obtained were as shown in Table 7.

Table 7 Temperature of measurement (C.) Condition 20 120 Initial 1500 kg/cm 1300 kg/cm After heated at 150C. for 30 days I650 kg/cm 1350 kg/cm EXAMPLE 3 Epoxy resin compositions (Sample Nos. 6 to 10) were prepared by mixing 100 parts by weight of an epoxy resin (Epikote 828, Shell Chemical Co.; epoxy equivalent, about 190) comprising diglycidyl ether of 20 bisphenol-A as the major constituent, 89 parts by weight of a curing agent (MI-IAC-P, Hitachi Chemical Co.) comprising methylbicyclo (2,2,1 )heptene-2,3- dicarboxylic acid anhydride as the major constituent,

aliphatic epoxy resin (Chissonox 221, Chisso Co., epoxy equivalent, 133), parts by weight of MHAC- P65, and 0.5 part by weight of an imidazolium tetrasubstituted borate shown in Table 8.

COMPARATIVE EXAMPLE 2 Epoxy resin compositions (Samples No. 14 and No. 15) were prepared by mixing parts by weight of Epikote 828, 89 parts by weight of MHAC-P, and 0.5 part by weight of a known curing catalyst shown in Table 9.

COMPARATIVE EXAMPLE 3 Table 8 (Examples 3 and 4) Potting Potting life/ Sample Gel time (hour) life gel time No. ITPB 150C. C. 100C. (hour) G 150C. G 120C.

6 lmidazolium tetraphenyl- 0.2 0.7 2.1 725 207 borate 2-EthyI-4-methyl- 7 imidazolium tetra- 0.2 0.9 2.9 250 1250 280 phenylborate l-Cyanoethyl-Z-ethyl- 8 4-methy1imidazol1um 0.2 1.0 3 .5 240 1200 240 tetraphenylborate l-Cyanoethyl-Z-un- 9 decylimidazolium 0.2 0.9 3.2 215 1075 239 tetraphenylborate l-Cyanoethyl-Z-phenyll0 imidazolium tetra- 0.2 0.9 3.0 210 1050 233 phenylborate 1 l Imidazolium tetraphenylborate 0.1 0.2 0.6 40 400 200 2-Ethyl-4-methyll2 imidazolium tetraphenyl- 0.15 0.4 0.9 45 300 1 12 borate l-Cyanoethyl-Z-ethyll3 4-methylimidazolium 0.2 0.8 1.4 45 225 56 tetraphenylborate Table 9 (Comparative Examples 2 and 3) Potting Potting life/ Sample Gel time (hour) life gel time No. Curing agent C. 120C. 100C. (hour) G 150C. G 120C.

14 Imidazole 0.2 0.5 1.5 45 225 90 2-Ethy1-4-methyll5 imidazole 0.2 0.6 2.0 60 300 100 16 Imidazole 0.15 0.5 1.0 25 167 50 2-Ethyl-4-methyll7 imidazole 0.2 0.7 2.3 36 51 Note: In the column ofpntting life/gel time" in Table 8 and Table 9, G150C. means the ratio of potting life to gel time at 150C.. and G 120C. means the ratio of potting life to gel time at 120C.

and 1 part by weight of an imidazolium tetrasubstituted borate shown in Table 8.

EXAMPLE 4 Epoxy resin compositions (Sample Nos. 1 1 to 13) were obtained by mixing 100 parts by weight of a cyclospectively.

Table 10 Item of test Tan 8(%) e p(Q-cm) I Sample No. 25C 80C. 120C. 25C. 80C. 120C. 25C. 80C. 120C.

7 0.3 0.5 1.2 3.4 3.6 3.8 10 3 X 1o 5 x 10 15 0.4 0.8 5.5 3.8 4.2 5.0 l0' 2 X 10 8 X 10 Note: In Table 10, the values of tan 8 and s were obtained by measurement at 60 Hz.

Table 11 Table l2 l Amine-type Item of Tensile Elon- Modulus of Heat dis- Epoxy resin curing agent lTPB test strength gation elasticity tortion Sample (parts by (parts by (parts by Sample temp. No. weight) weight) weight) No. (kglcm (kglcm (C.)

Methylenebis(o- 7 530 13 X 128 15 18 Epikote 1001 chloroaniline) 15 350 85 1.1 10 115 100 13 4 lmidazolium Note: The values of tensile strength, elongation, and modulus of elasticity given in 19 tetra henyl- Table 11 were obtained by measurement at 100C. borate EXAMPLE 5 2-Methylimida- 20 20 zolium tetra- An epoxy resm composition for use as an adhesive phenylbo ate was prepared by uniformly mixing 100 parts by weight 2 Ph of vinylcyclohexene dioxide (Chissonox 206, Chisso 21 'l H 3'g Co.; epoxy equivalent, 76), 100 parts by weight of phenylborate hexahydrophthalic anhydride, 3 parts by weight of 2- i ethyl-4-methylimidazolium tetraphenylborate, and 22 metMlimida. 2,300 parts by weight of powdered zirconium silicate z i which had been surface-treated with a coupling agent p z' comprising y-glycidoxypropyltrimethoxysilane. The 2-Ethyl-4- composition obtained was sufficiently usable even after P o 3O 23 ZO11L11T1 tetrahavmg been stored at 25 C. for 3 months or more, indi- Nbuwmorate eating a good storage stability.

Th dh .t. th bt d d t Diamlnodie a esive composl ion us o a ne was use 0 24 I phenyl sulfone bond two ceramic rods, 300 mm in diameter, to each (12.4 other. Curing was conducted for 10 hours at 60C., and i o methyhmldafor a further 3 hours at 150 C. The linear thermal ex- 2 zolium tetrapansion coefficient (a) of the cured adhesive was 9.6 Phenylbowte X l0 /C. (the linear thermal expansion coefficient of 26 H Dicyandiamide i the ceramic rods itself being 5.3 X 10 /C.). The flex- (100 (4.2 ural strength of the bonded portion was 1,700 kg/cm y -fi- 2 4O methyhmida- (mltial), 610 kg/cm after having been immersed in 27 zolium mm boiling water for 100 hours, and 680 kg/cm after havphenylborate ing been subjected to a 100-cycle of thermal shock test, M ethylenebmm (2) one cycle consisting of an exposure to a temperature of 28 ECN-1273 chloroaniline) 100C. for 2 hours followed by allowing to stand at (100) (27-7) 50C f 2 h 2-Ethyl-4- or oursmethylimida- As is apparent from the above results, the epoxy resm 29 zolium tetracomposition of this invention had a good adhesive z'gf strength comparable to that of a conventional adhesive, 30 DER-511 and, moreover, was sufficiently satisfactory in both (100) (15-8) 2 Em I 4 storage stability and curability, which is the main object H of this invention. 31 zolium tetraphenylborate EXAMPLE 6 (5) Epoxy resin compositions (Sample Nos. 19 to 23, 25, 27, and 31) were obtained by dissolving various solid epoxy resins, amine-type curing agents, and ITPB In methyl Cellosolve according to the formulations shown in Table 12 so that the solids content of the composition became 50 by weight. Each of the compositions thus obtained was tested for the gel time at 170C. and 200C. and for the potting life when kept in a closed vessel at 40C. The results obtained were as shown in Table 13. The potting life was shown, as mentioned above, in terms of days which had elapsed before the viscosity of the resin composition reached a value 10 times the initial viscosity value (viscosity at the time of preparation). In Tables 12 and 13, there are also shown comparative examples (Sample Nos. 18, 24, 26, 28 and 30) wherein ITPB was not used.

Note: In Table 12, Epikote 1001 is a bisphenol-A diglycidyl ether-type epoxy resin (epoxy equivalent 456) produced by Shell Chemical Co; ECN-l273 is a novo1ac-based epoxy resin (epoxy equivalent 242) produced by ClBA Ltd.; and DER-5 l 1 is a brominated bisphenol-A diglycidyl ether-type epoxy resin (epoxy equivalent 48S) produced by Dow Chemical Co.

EXAMPLE 7 Epoxy resin compositions (Sample Nos. 33, 35, and 37) were obtained according to the formulations given in Table 14 by dissolving an amine-type curing agent in a liquid epoxy resin, and adding to the resulting solution, after having been cooled, an ITPB to dissolve therein. The gel times and potting lives of the resin compositions thus obtained were as shown in Table 15. In Tables 14 and 15, there are also shown comparative examples (Sample Nos. 32, 34 and 36) wherein no ITPB was used.

Table 14 Amine-type Epoxy resin curing agent ITPB Sample (parts by (parts by (Parts by No. weight) weight) weight) Methylenebis(o- 32 Epikote 828 chloroaniline) 2-Ethyl-4 methylimida- 33 zolium tetraphenylborate Diaminodiphenyl- 34 methane 2-Ethy1-4- methylimida- 35 zolium tetraphenylborate 36 Dicyandiamide 2-Etl1yl-4- methylimida- 37 zolium tetraphenylborate Table Sample Gel time (min.) Potting life No. 170C. 200C. (day) Note: In Table 15, Epikote 828" is a liquid epoxy resin of the bisphenoLA diglycidyl ether type (epoxy equivalent, 197) produced by Shell Chemical Co.

COMPARATIVE EXAMPLE 4 According to the formulations given in Table 16, methyl Cellosolve solutions (varnish) (Sample Nos. 38 to 43) containing an epoxy resin, amine-type curing agent, and curing catalyst were prepared. The gel times and potting lives of the varnishes thus obtained were as shown in Table 17.

Table 16 Amine-type Epoxy resin curing agent Curing catalyst Sample (parts by (parts by (parts by No. weight) weight) weight) Methylenebis(o 2 Ethyl-4- 38 Epikote 1001 chloroaniline) methylimida- (100) (13.4) zole 39 BF -monoethylamine compound 2-Ethyl-4- 40 ECN1273 methylimida- (100) (27.7) zole (0.5) 4 1 BF -monoethylamine compound (05) 2-Ethyl-4- 42 DER-51 1 methylimi- (100) (15.8) dazole BF -monoethyl- 43 amine compound Table 17 Sample Gel time (min.) Potting life No. 170C. 200C. (day) EXAMPLE 8 A piece of glass cloth was impregnated with the varnish shown in Table 18 and dried at C. for 10 minutes to prepare a prepreg having a resin content of about 55 In Table 18 is also shown the formulation of Comparative Example 5.

Five sheets of each of the prepregs obtained in Example '8 and Comparative Example 5 were pressed at C. under pressure of 50 kg/cm for 1 hour to yield laminated sheets, 0.6 mm in thickness. The laminated sheets were evaluated for the moisture resistance which is believed to be most adversely affected by a BF amine compound. The evaluation was made by inspecting the appearance of the laminated sheet after having been immersed in boiling water. The results obtained were as shown in Table 19.

Table 19 Test Duration of immersion condition in boiling water Sample 30 minutes 1 hour 4 hours Example 8 No change No change No change Comparative Local Mcasling all Example 5 measling over the surface As is apparent from Table 19, when an imidazolium tetra-substituted borate was used according to this invention, the moisture resistance of the laminate presented no problem at all, whereas when a conventional BF -amine compound was used, the reduced moisture resistance of the laminate presented a difficult problem. The laminate obtained in Example 8 is also favorably comparable to that obtained from a conventional composition in electrical and mechanical properties and in thermal stability. The prepreg obtained in Example 8 also showed little change after having been allowed to stand at room temperature for more than 3 months, indicating a good storage stability.

As is apparent from the foregoing Examples and Comparative Examples, the accelerating effect of ITPB on curing reaction of an epoxy resin composition containing a curing agent of the acid anhydride type or the amine type is manifested hardly at room temperature but markedly at elevated temperatures. It has been known and also confirmed by Sample Nos. 39, 41, and 43 that a conventional boron trifluoride-amine complex is a curing catalyst also capable of showing a socalled latent curing ability. However, a cured product obtained by using a boron trifluoride-arnine complex has a problem in moisture resistance, and hence, the range of its use is restricted. According to this invention, there is no problem about the moisture resistance, while a reduced moisture resistance of the cured product is the greatest disadvantage of boron trifluorideamine complexes. The present composition is comparable favorably to a conventional composition containing a boron trifluoride-amine complex in electrical and mechanical properties of the cured product, and no problem is raised in this respect.

Z-Heptadecylimidazolium 3 tetraphenylborate Zinc terephthalate 5 Camauba wax 3 Carbon l Powdered silica 5 EXAMPLE 1 1 Parts by s a. Cresol-novolac-based epoxy lOO resin (epoxy equivalent, 235) b. Tetrahydrophthalic anhydride 60 c. 2-Ethyl-4-methylimidazolium 3 e. Stearic acid 2 f. Carbon 1 g. Powdered silica 400 EXAMPLE 12 Parts by weight a. Phenol-novolac-based epoxy resin (epoxy equivalent, 230) b. Hexahydrophthalic anhydride 50 c. Z-Heptadecylimidazolium 3 tetraphenylborate 3 e. Camanba wax 3 f. Carbon 1 g. Powdered silica 450 COMPARATIVE EXAMPLE 6 Parts by weight a. Phenol-novolac-based epoxy resin (epoxy equivalent, 230) b. Hexahydrophthalic anhydride 50 c. 2-Heptadecylimidazole 3 (curing promoter) 3 e. Camanba wax 3 f. Carbon 1 g. Powdered silica 450 COMPARATIVE EXAMPLE 7 Parts by weight a. Cresol-novolac-based epoxy I00 resin (epoxy equivalent, 235) b. Tetrahydrophthalic anhydride 60 c. Boron trifluoride-mono- 3 ethylamine e. Stearic acid 2 f. Carbon 1 g. Powdered quartz glass 400 Each of the formulations given in the foregoing Examples 9 to 12 and Comparative Examples 6 and 7 was blended with a mixing roll at 50 to 80C. for 10 to 15 minutes, cooled, and pulverized.

By using the epoxy resin composition thus obtained, a modified field effect semiconductor integrated circuit device (modified FET-type IC) was encapsulated by transfer molding at C. for 3 minutes. The encapsulated modified PET-type [C was tested for temperature dependency of the leakage current due to a parasitic channel in the following way. Under predetermined temperature conditions, a voltage of -24 V was applied to the gate for 1 hour, then a voltage of 12 V was applied between drain and source, and immediately thereafter the gate voltage was released. At the same time, the maximum leakage current which flowed between the source and drain (I was measured. The results obtained were as shown in Table 20.

Table 20 Leakage current, I (,uA) Sample 20C. 50C. 65C. 80C. IC. l 20C. 150C.

Example 9 0 O 0 0 0 4 18 Example 10 0 0 0 O 0 6 25 Example I l 0 0 0 l 30 255 600 Example 12 0 0 l 25 200 550 Comparative Example 6 0 I 50 250 500 650 300 Comparative Example 7 0 5 70 300 550 670 200 EXAMPLE l3 EXAMPLE 17 Parts by Parts by weight weight a. o-Cresol-novolac-based epoxy a. Bisphenol-A-based epoxy resin (ECN 1299, CHIBA Ltd.; 100 resin (Epikote 1001, Shell epoxy equivalent, 235) Chemical Co.', epoxy equivalent, 100 b. 3,3'-Dichlorodiaminodi- 40 400) phenylmethane 20 b. 3,3"Dichlorodiaminodiphenylc. lmidazole tetraphenylborate 3 methane 35 -k; id 2 c. 2-Ethyl-4-methylimidazolium 5 f Carbon 3 tetraphenylborate g. Powdered quartz glass 390 acid 3 f. Carbon 1 g. Powdered alumina 1,000

EXAMPLE 14 COMPARATIVE EXAMPLE 8 Paris by Parts by weight weight a. Phenol-novolac-based epoxy ECN I299 '00 'N b. 3,3'Dichlorodiaminodiphenyl- 40 Carbide Corp.; epoxy equi- 100 methane valent, 230) c. Z-Heptadecylimidazole 3 b. 3,3 -Drammodiphenyl sulfone Stearic acid 2 c. 2-Ethyl-4-methylimidazolium 4 Carbon telmphenylbome 35 g. Powdered quartz glass 390 e. Stearic acid 2 1. Carbon 0.5 g. Zirconium silicate 1,000 h. 'y-Glyeidoxypropyltrimethoxy- 2 COMPARATIVE EXAMPLE 9 silane 40 Parts by weight EXAMPLE 15 a. ERR 0100 100 bv 3,3'-Diaminodiphenyl sulfone 35 c. 2-Ethyl-4-methylimidazole 4 b e. Stearic acid 2 Panfs y 1. Carbon 0.5

we'gm g. Zirconium silicate 1,000 a. Bisphenol-A-based epoxy h. -y-Glycidoxypropyltrimethoxy- 2 resin (Epikote 1004, Shell 100 silane Chemical; epoxy equivalent, 1,500) b. Diaminodiphenylmethane 10 c cyanethy| 2 elhyl 4 COMPARATIVE EXAMPLE l0 methylimidazolium tetraphenylborate e. Hoechst wax 3 parts by f. Carbon 1 weight g Calcium carbonate 800 a Epikote 1004 100 b. Diaminodiphenylmethane 10 c. 2-Undecylimidazo1e 3 e. Hoechst wax 3 EXAMPLE 16 Carbon 1 g. Calcium carbonate 800 P rrs b j COMPARATIVE EXAMPLE 11 a. Heterocyclic epoxy resin 7 (T GlC, CHlBA Ltd.; epoxy equivalent, P3113 y b. 3,3'-Dichlorodiaminodiphenyl- 60 Welght methane a. ECN 1273 100 c. l Cyanoethyl-2-phenylimidazolium 5 5 b, Diaminodiphenylmethane 25 tetraphenylborate d. Zinc salicylate 0.5 e. Camauba wax 3 e. Stean'c acid 2 1. Carbon 1 1. Carbon 1 g. Powdered quartz glass 550 g. Powdered quartz glass 230 Each of the formulations shown in the foregoing Examples 13 to 17 and Comparative Examples 8 to 11 was blended with a mixing roll at 70 to 75C. for minutes to prepare an epoxy resin composition.

Potting lives at 25C. of the resin compositions thus obtained were as shown in Table 21. On the other hand, in order to confirm uniform dispersion of powdered inorganic fillers throughout the resin composition, a semiconductor integrated circuit device was encapsulated with the resin composition by transfer molding and subjected to the heat cycle test to examine connection failure. Transfer molding was carried out at 165C. for 3 minutes and the molded device was heated at 150 to 170C. for 5 hours to finish curing of the resin. The thermal shock test was continued until connection failure took place in an inner lead wiring, and the number of thermal cycles was recorded to evaluate the dispersion of fillers [one thermal cycle consisted of an exposure to a temperature of 150C. for 2 min. and cooling at l90C. for 2 min. (in liquid nitrogen)]. In Table 21, the samples obtained in Comparative Examples 8 to 1 l were marked with A and B to indicate duration of mixing. In A, the mixing time is 2 to 3 minutes As seen from Table 21, the compositions of Examples 13 to 17 are excellent in both potting life and thermal shock characteristics. This means that favorable results are obtained in the thermal shock test because sufficiently uniform mixing of inorganic fillers and other ingredients has been ensured by wet mixing, and that such an intensive mixing has not brought about a decrease in potting life. To the contrary, in the case of the compositions of Comparative Examples 8 to 11, if the mixing time is kept short to avoid decrease in potting life, undesirable results are obtained in the thermal shock test, as seen from each A, because the ingredients, particularly powdered inorganic fillers, is not uniformly mixed, while if the mixing is sufficiently carried out, the potting life decreases so much that the composition becomes unsuitable for practical use, as shown by B.

What we claim is:

1. An epoxy resin composition consisting essentially of (a) 100 parts by weight of an epoxy resin having at least two vicinal epoxy groups and (b) 0.01 to 30 parts by weight of at least one organoboron compound selected from the group consisting of tetraphenyl borates of imidazole and tetraphenylborates of imidazole derivatives obtained by reacting alkali metal salts of tetraphenylboron with at least one member selected from the group consisting of salts of imidazole and salts of imidazole derivatives obtained by reacting imidazole or an imidazole derivative represented by the general formula:

wherein R R R and R which may be same as or different from one another, are selected from the group consisting of hydrogen, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, acyl groups having 2 to 7 carbon atoms, aryl groups having 6 to 12 carbon atoms, cycloalkyl groups having 6 to 12 carbon atoms, cycloalkenyl groups having 6 to 12 carbon atoms, aldehyde group, carboxyl group, cyano group, and nitro group, with acids.

2. An epoxy resin composition according to claim 1, wherein the amount of the at least one organoboron compound (b) is 0.5 to 20 parts by weight.

3. An epoxy resin composition consisting essentially of (a) parts by weight of an epoxy resin having at least two vicinal epoxy groups, (b) 0.01 to 30 parts by weight of at least one organoboron compound selected from the group consisting of tetraphenylborates of imidazole and tetraphenylborates of imidazole derivatives obtained by reacting alkali metal salts of tetraphenylboron with at least one member selected from the group consisting of salts of imidazole and salts of imidazole derivatives formed by reacting imidazole or imidazole derivatives represented by the general formula:

at I

wherein R R R and R.,, which may be the same as or different from one another, are selected from the group consisting of hydrogen, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2m 6 carbon atoms, acyl groups having 2 to 7 carbon atoms, aryl groups having 6 to 12 carbon atoms, cycloalkyl groups having 6 to 12 carbon atoms, cycloalkenyl groups having 6 to 12 carbon atoms, aldehyde group, carboxyl group, cyano group, and nitro group, with acids, and (c) 0.1 to 200 parts by weight of a curing agent selected from the group consisting of acid anhydrides and amine compounds.

4. An epoxy resin composition according to claim 3, wherein the amount of the at least one organoboron compound (b) is 0.01 to 20 parts by weight; the curing agent (c) is an acid anhydride and the amount of said acid anhydride is 0.1 to 200 parts by weight.

5. An epoxy resin composition according to claim 3, wherein the amount of the at least one organoboron compound (b) is 0.01 to 20 parts by weight; the curing agent (c) is an amine compound and the amount of said amine compound is 0.1 to parts by weight.

6. An epoxy resin composition according to claim 1, wherein the organoboron compound (b) is at least one member selected from the group consisting of imidazolium tetraphenylborate, 2-ethyl-4- methylimidazolium tetraphenylborate, l-cyanoethyl-2- phenylimidazolium tetraphenylborate, l-cyanoethyl-2- undecylimidazolium tetraphenylborate, l-cyanoethyl- 2-ethyl-4-methylimidazolium tetraphenylborate, and 2-ethyl-l ,4-dimethylimidazolium tetraphenylborate.

7. An epoxy resin composition according to claim 3, wherein the organoboron compound (b) is at least one tetraphenylborate selected from the group consisting of imidazolium tetraphenylborate, 2-ethyl-4- methylimidazolium tetraphenylborate, l-cyanoethyl-2- phenylimidazolium tetraphenylborate, l-cyanoethyl-2- undecylimidazolium tetraphenylborate, l-cyanoethyL 2-ethyl-4-methylimidazolium tetraphenylborate, and 2-ethyll ,4-dimethylimidazolium tetraphenylborate.

8. An epoxy resin composition according to claim 3, wherein the curing agent (c) is at least one member selected from the group consisting of maleic anhydride, dichloromaleic anhydride, dodecenylsuccinic anhydride, pyromellitic dianhydride, trimellitic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride, m-phenylenediamine, diaminodiphenyl ether, diaminodiphenylmethane, 4,4 diaminodiphenylmethane-3,3'-dicarbonic acid, diaminodiphenyl sulfone, benzidine, 4,4-bis(o-toluidine), 4,4'-thiodianiline, dianisidine, methylenebis(ochloroaniline), bis(3,4-diaminophenyl) sulfone, and diaminoditolyl sulfone.

9. An epoxy resin composition according to claim 4, wherein the curing agent (c) is at least one acid anhydride selected from the group consisting of maleic anhydride, dichloromaleic anhydride, dodecenylsuccinic anhydride, pyromellitic dianhydride, trimellitic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, and hexachloroendomethylenetetrahydrophthalic anhydride.

10. An epoxy resin composition according to claim 5, wherein the curing agent (c) is at least one aromatic amine compound selected from the group consisting of m-phenylenediamine, diaminodiphenyl ether, diaminodiphenylmethane, 4,4-diaminodiphenylmethane-3,3'- dicarbonic acid, diaminodiphenyl sulfone, benzidine, 4,4-bis(o-toluidine), 4,4'-thiodianiline, dianisidine, methylene-bis(o-chloroaniline bis( 3 ,4- diaminophenyl) sulfone, and diaminoditolyl sulfone.

11. An epoxy resin composition comprising (a) 100 parts by weight of an epoxy resin having at least two vicinal epoxy groups, (b) 0.01 to parts by weight of at least one organoboron compound selected from the group consisting of tetraphenyl borates of imidazole and tetraphenylborates of imidazole derivatives obtained by reacting alkali metal salts of tetraphenylboron with at least one member selected from the group consisting of salts of imidazole and salts of imidazole derivatives formed by reacting imidazole or imidazole derivatives represented by the general formula:

wherein R R R and R which may be the same as or different from one another, are selected from the group consisting of hydrogen, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, acyl groups having 2 to 7 carbon atoms, aryl groups having 6 to 12 carbon atoms, cycloalkyl groups having 6 to 12 carbon atoms, cycloalkenyl groups having 6 to 12 carbon atoms, aldehyde group, carboxyl group, cyano group, and nitro group, with acids, and (d) 0.01 to 10 parts by weight of a curing catalyst for use in epoxy resins.

12. An epoxy resin composition'according to claim 1, comprising at least one inorganic filler selected from the group consisting of glass, quartz glass, mica, calcium carbonate, calcium sulfate, barium sulfate, alumina, talc, clay, zirconium silicate (zircon), zirconium oxide, lithium aluminum silicate, beryl, aluminum silicate, beryllia, calcium silicate, and silica.

13. An epoxy resin composition according to claim 3, which further contains at least one inorganic filler selected from the group consisting of glass, quartz glass, mica, calcium carbonate, calcium sulfate, barium sulfate, alumina, talc, clay, zirconium silicate (zircon), zirconium oxide, lithium aluminum silicate, beryl, aluminum silicate, beryllia, calcium silicate, and silica.

14. A method for manufacturing an epoxy resin com position, which comprises bringing a mixture of starting materials into a softened or molten state by heating at 40 to C. and subjecting the softened or molten mixture to a mixing treatment while applying a shearing force, said mixture of the starting materials comprising (a) parts by weight of an epoxy resin having at least two vicinal epoxy groups, (b) 0.01 to 30 parts by weight of at least one organoboron compound selected from the group consisting of tetraphenylborates of imidazole and tetraphenylborates of imidazole derivatives obtained by reacting alkali metal salts of tetraphenylboron with at least one member selected from the group consisting of salts of imidazole and salts of imidazole derivatives formed by reacting imidazole or imidazole derivatives represented by the general formula:

wherein R R R and R which may be the same as or different from one another, are selected from the group consisting of hydrogen, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, acyl groups having 2 to 7 carbon atoms, aryl groups having 6 to 12 carbon atoms, cycloalkyl groups having 6 to 12 carbon atoms, cycloalkenyl groups having 6 to 12 carbon atoms, aldehyde group, carboxyl group, cyano group, and nitro group, with acids, and (c) 0.1 to 200 parts by weight of a curing agent selected from acid anhydrides and amine compounds.

treatment is carried out by means of a mixing roll, a Kokneader-type extruder, a ribbon mixer, or an extruder.

17. A method for manufacturing an epoxy resin composition according to claim 14, wherein the epoxy resin (a), the organoboron compound (b), and the curing agent are compounded with an inorganic filler. 

1. AN EPOXY RESIN COMPOSITION CONSISTING ESSENTIALLY OF (A) 100 PARTS BY WEIGHT OF AN EPOXY RESIN HAVING AT LEAST TWO VICINAL EPOXY GROUPS AND (B) 0.01 TO 30 PARTS BY WEIGHT OF AT LEAST ONE ORGANOBORON COMPOUND SELECTED FROM THE GROUP CONSISTING OF TETRAPHENYL BORATES OF IMIDAZOLE AND TETRAPHENYLBORATES OF IMIDAZOLE DERIVATIVES OBTAINED BY REACTING ALKALI METAL SALTS OF TETRAPHENYLBORON WITH AT LEAST ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF SALTS OF IMIDAZOLE AND SALTS OF IMIDAZOLE DERIVATIVES OBTAINED BY REACTING IMIDAZOLE OR AN IMIDAZOLE DERIVATIVE REPRESENTED BY THE GENERAL FORMULA:
 2. An epoxy resin composition according to claim 1, wherein the amount of the at least one organoboron compound (b) is 0.5 to 20 parts by weight.
 3. An epoxy resin composition consisting essentially of (a) 100 parts by weight of an epoxy resin having at least two vicinal epoxy groups, (b) 0.01 to 30 parts by weight of at least one organoboron compound selected from the group consisting Of tetraphenylborates of imidazole and tetraphenylborates of imidazole derivatives obtained by reacting alkali metal salts of tetraphenylboron with at least one member selected from the group consisting of salts of imidazole and salts of imidazole derivatives formed by reacting imidazole or imidazole derivatives represented by the general formula:
 4. An epoxy resin composition according to claim 3, wherein the amount of the at least one organoboron compound (b) is 0.01 to 20 parts by weight; the curing agent (c) is an acid anhydride and the amount of said acid anhydride is 0.1 to 200 parts by weight.
 5. An epoxy resin composition according to claim 3, wherein the amount of the at least one organoboron compound (b) is 0.01 to 20 parts by weight; the curing agent (c) is an amine compound and the amount of said amine compound is 0.1 to 150 parts by weight.
 6. An epoxy resin composition according to claim 1, wherein the organoboron compound (b) is at least one member selected from the group consisting of imidazolium tetraphenylborate, 2-ethyl-4-methylimidazolium tetraphenylborate, 1-cyanoethyl-2-phenylimidazolium tetraphenylborate, 1-cyanoethyl-2-undecylimidazolium tetraphenylborate, 1-cyanoethyl-2-ethyl-4-methylimidazolium tetraphenylborate, and 2-ethyl-1,4-dimethylimidazolium tetraphenylborate.
 7. An epoxy resin composition according to claim 3, wherein the organoboron compound (b) is at least one tetraphenylborate selected from the group consisting of imidazolium tetraphenylborate, 2-ethyl-4-methylimidazolium tetraphenylborate, 1-cyanoethyl-2-phenylimidazolium tetraphenylborate, 1-cyanoethyl-2-undecylimidazolium tetraphenylborate, 1-cyanoethyl-2-ethyl-4-methylimidazolium tetraphenylborate, and 2-ethyl-1,4-dimethylimidazolium tetraphenylborate.
 8. An epoxy resin composition according to claim 3, wherein the curing agent (c) is at least one member selected from the group consisting of maleic anhydride, dichloromaleic anhydride, dodecenylsuccinic anhydride, pyromellitic dianhydride, trimellitic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride, m-phenylenediamine, diaminodiphenyl ether, diaminodiphenylmethane, 4,4''-diaminodiphenylmethane-3,3''-dicarbonic acid, diaminodiphenyl sulfone, benzidine, 4,4''-bis(o-toluidine), 4,4''-thiodianiline, dianisidine, methylenebis(o-chloroaniline), bis(3,4-diaminophenyl) sulfone, and diaminoditolyl sulfone.
 9. An epoxy resin composition according to claim 4, wherein the curing agent (c) is at least one acid anhydride selected from the group consisting of maleic anhydride, dichloromaleic anhydride, dodecenylsuccinic anhydride, pyromellitic dianhydride, trimellitic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydrIde, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, and hexachloroendomethylenetetrahydrophthalic anhydride.
 10. An epoxy resin composition according to claim 5, wherein the curing agent (c) is at least one aromatic amine compound selected from the group consisting of m-phenylenediamine, diaminodiphenyl ether, diaminodiphenylmethane, 4,4''-diaminodiphenylmethane-3,3''-dicarbonic acid, diaminodiphenyl sulfone, benzidine, 4,4''-bis(o-toluidine), 4,4''-thiodianiline, dianisidine, methylene-bis(o-chloroaniline), bis(3,4-diaminophenyl) sulfone, and diaminoditolyl sulfone.
 11. An epoxy resin composition comprising (a) 100 parts by weight of an epoxy resin having at least two vicinal epoxy groups, (b) 0.01 to 30 parts by weight of at least one organoboron compound selected from the group consisting of tetraphenyl borates of imidazole and tetraphenylborates of imidazole derivatives obtained by reacting alkali metal salts of tetraphenylboron with at least one member selected from the group consisting of salts of imidazole and salts of imidazole derivatives formed by reacting imidazole or imidazole derivatives represented by the general formula:
 12. An epoxy resin composition according to claim 1, comprising at least one inorganic filler selected from the group consisting of glass, quartz glass, mica, calcium carbonate, calcium sulfate, barium sulfate, alumina, talc, clay, zirconium silicate (zircon), zirconium oxide, lithium aluminum silicate, beryl, aluminum silicate, beryllia, calcium silicate, and silica.
 13. An epoxy resin composition according to claim 3, which further contains at least one inorganic filler selected from the group consisting of glass, quartz glass, mica, calcium carbonate, calcium sulfate, barium sulfate, alumina, talc, clay, zirconium silicate (zircon), zirconium oxide, lithium aluminum silicate, beryl, aluminum silicate, beryllia, calcium silicate, and silica.
 14. A method for manufacturing an epoxy resin composition, which comprises bringing a mixture of starting materials into a softened or molten state by heating at 40* to 85*C. and subjecting the softened or molten mixture to a mixing treatment while applying a shearing force, said mixture of the starting materials comprising (a) 100 parts by weight of an epoxy resin having at least two vicinal epoxy groups, (b) 0.01 to 30 parts by weight of at least one organoboron compound selected from the group consisting of tetraphenylborates of imidazole and tetraphenylborates of imidazole derivatives obtained by reacting alkali metal salts of tetraphenylboron with at least one member selected from the group consisting of salts of imidazole and salts of imidazole derivatives formed by reacting imidazole or imidazole derivatives represented by the general formula:
 15. A method for manufacturing an epoxy resin composition according to claim 14, wherein the epoxy resin (a) is a solid epoxy resin, the curing agent (c) is an amine compound, and the amount of said amine compound is 0.1 to 150 parts by weight.
 16. A method for manufacturing an epoxy resin composition according to claim 14, wherein the mixing treatment is carried out by means of a mixing roll, a Ko-kneader-type extruder, a ribbon mixer, or an extruder.
 17. A method for manufacturing an epoxy resin composition according to claim 14, wherein the epoxy resin (a), the organoboron compound (b), and the curing agent are compounded with an inorganic filler. 